DK155020B - PROCEDURE FOR RECOVERING MOLYBDA IN THE FORM OF Aqueous SOLUTION OF PURE MOLYBDAIC ACID FROM MOLYBDA-CONTAINING CATALYSTS - Google Patents
PROCEDURE FOR RECOVERING MOLYBDA IN THE FORM OF Aqueous SOLUTION OF PURE MOLYBDAIC ACID FROM MOLYBDA-CONTAINING CATALYSTS Download PDFInfo
- Publication number
- DK155020B DK155020B DK539380AA DK539380A DK155020B DK 155020 B DK155020 B DK 155020B DK 539380A A DK539380A A DK 539380AA DK 539380 A DK539380 A DK 539380A DK 155020 B DK155020 B DK 155020B
- Authority
- DK
- Denmark
- Prior art keywords
- molybdenum
- acid
- solution
- aqueous solution
- pure
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
DK 155020 BDK 155020 B
Opfindelsen angår en fremgangsmåde til genvinding af molybdæn i form af en vandig opløsning af ren molybdæn-syre fra brugte molybdænholdige katalysatorer til oxidering af methanol til formaldehyd eller brugte hydrogene-5 ringskatalysatorer indeholdende molybdænoxid samt even tuelt cobalt- og/ellér nikkeloxider, ved hvilken katalysatorerne i et første trin udludes med en vandig opløsning af et alkalimetalhydroxid til dannelse af en vandig alka-limetalmolybdatopøsning, hvorefter denne i et andet 10 trin renses og konverteres til en ren vandig opløsning af molybdænsyre.The invention relates to a process for the recovery of molybdenum in the form of an aqueous solution of pure molybdenum acid from spent molybdenum-containing catalysts for the oxidation of methanol to formaldehyde or used hydrogenation catalysts containing molybdenum oxide, and optionally cobalt and / or nickel catalysts, in a first step, an aqueous solution of an alkali metal hydroxide is precipitated to form an aqueous alkali metal molybdate solution, after which in a second step it is purified and converted to a pure aqueous solution of molybdenum acid.
Molybdænforbindelser anvendes i vid udstrækning inden for teknikken, specielt som komponenter i hydrogeneringskatalysatorer eller katalysatorer, der egner sig til 15 oxidering af methanol til formaldehyd. Genvinding af molybdæn i ren form og med højt udbytte fra disse brugte katalysatorer er derfor et praktisk problem af stor betydning, dels fordi molybdæn er særdeles kostbart, dels af økologiske grunde.Molybdenum compounds are widely used in the art, especially as components of hydrogenation catalysts or catalysts suitable for the oxidation of methanol to formaldehyde. Recovery of molybdenum in pure form and with high yield from these used catalysts is therefore a practical problem of great importance, partly because molybdenum is extremely expensive, and partly for ecological reasons.
20 Forskellige fremgangsmåder til genvinding af molybdæn-forbindelser er kendte inden for teknikken.Various methods for recovering molybdenum compounds are known in the art.
Ifølge engelsk patentskrift nr. 350 135 kan man således behandle blandinger af molybdæn eller molybdænforbindelser med andre metaller eller metalforbindelser med oxygen 25 eller en gasart, der indeholder molekylært oxygen ved forhøjede temperaturer og sædvanligvis indtil ca. 600 °C, hvorefter molybdænoxiderne adskilles fra blandingerne, der stammer fra denne behandling. Ifølge USA patentskrift nr. 3 538 017 pulveriseres og udglødes de brugte katalysa-30 torer baseret på molybdæn- og jernoxider, hvorefter det udglødede pulver behandles med vandig ammoniak, hvorved der dannes en opløsning af molybdænsalt. Fra den således fremstillede opløsning fjernes den overskydende ammoniak i forhold til den støkiometrisk nødven-Thus, according to British Patent No. 350 135, mixtures of molybdenum or molybdenum compounds can be treated with other metals or metal compounds with oxygen or a gas containing molecular oxygen at elevated temperatures and usually up to approx. 600 ° C, after which the molybdenum oxides are separated from the mixtures resulting from this treatment. According to US Patent No. 3 538 017, the spent catalysts based on molybdenum and iron oxides are pulverized and annealed, after which the annealed powder is treated with aqueous ammonia to form a solution of molybdenum salt. From the solution thus prepared, the excess ammonia relative to the stoichiometric emergency valve is removed.
DK 155020BDK 155020B
2 dige mængde, hvorved der dannes ammoniummolybdat.2 amounts to form ammonium molybdate.
I USA patentskrift nr. 4 145 397 beskrives en fremgangsmåde til genvinding af bl.a. molybdæn og vanadium fra brugte katalysatorer anvendt til afsvovling af carbon-5 hydrider. Efter en oxiderende ristning ved 600 - 900 °C underkastes katalysatoren en alkalisk udludning, hvorved der fremkommer en stærkt alkalisk vandig vanadat-, aluminat- og molybdatopløsning med en pH-værdi større end 13, almindeligvis større end 14. pH-værdien af denne 10 opløsning sænkes derpå til en værdi i intervallet 11 - 13, fortrinsvis 11 - 12, uden tilsætning af kemikalier, f. eks. ved elektrodialyse eller behandling med en kation-bytter, hvorpå pH-værdien sænkes yderligere til 7,5 - 9,5, fortrinsvis til mellem ca. 8 og ca. 9, ved tilsæt- 15 ning af mineralsyre, hvorved aluminium fjernes fra opløs ningen ved udfældning af aluminiumhydroxid. Til sidst udfældes først vanadat og dernæst molybdat som ammoniumsalte ved tilsætning af vandopløselige ammoniumsalte.U.S. Patent No. 4,145,397 discloses a method of recovering e.g. molybdenum and vanadium from used catalysts used for desulfurization of hydrocarbons. After an oxidizing shake at 600 - 900 ° C, the catalyst is subjected to an alkaline leaching to produce a highly alkaline aqueous vanadate, aluminate and molybdate solution having a pH greater than 13, generally greater than 14. The pH of this solution is then lowered to a value in the range 11 - 13, preferably 11 - 12, without the addition of chemicals, for example, by electrodialysis or treatment with a cation exchanger, whereupon the pH is further lowered to 7.5 - 9.5 , preferably to between ca. 8 and approx. 9, by adding mineral acid, thereby removing aluminum from the solution by precipitation of aluminum hydroxide. Finally, vanadate and then molybdate are first precipitated as ammonium salts by the addition of water-soluble ammonium salts.
I tysk offentliggørelsesskrift nr. 2 631 089 beskrives 20 en fremgangsmåde til genvinding af molybdæn fra samme type katalysator, ved hvilken udludningen gennemføres på en speciel måde: Katalysatoren imprægneres med en koncentreret natriumhydroxidopløsning, hvorefter den imprægnerede katalysator kalcineres ved en temperatur 25 over 800 °C, hvorpå det kalcinerede produkt uden for udgående afkøling udhældes i vand. Herved fremkommer en vandig alkalisk molybdatopløsning, som indeholder mindre mængder aluminium. Efter udfældning af aluminium-hydroxid ved indstilling af pH-værdien på ca. 7 udfældes 30 calciummolybdat ved tilsætning af et opløseligt calciumsalt. Calciumsaltet omsættes endelig med salpetersyre til dannelse af molybdænsyre.German Publication No. 2,631,089 discloses a process for recovering molybdenum from the same type of catalyst in which the leaching is carried out in a special way: The catalyst is impregnated with a concentrated sodium hydroxide solution and the impregnated catalyst is calcined at a temperature above 25 ° C. , after which the calcined product outside the outgoing cooling is poured into water. This results in an aqueous alkaline molybdate solution containing smaller amounts of aluminum. After precipitation of aluminum hydroxide by adjusting the pH of approx. 7, 30 calcium molybdate is precipitated by the addition of a soluble calcium salt. The calcium salt is finally reacted with nitric acid to form molybdenum acid.
DK 155020 BDK 155020 B
33
Disse kendte fremgangsmåder frembyder ulemper, der skyldes de mange behandlingstrin og omkostningerne ved disse og yderligere de udbytter, hvormed molybdænet udvindes.These known methods present disadvantages due to the many processing steps and the costs thereof and further to the yields by which the molybdenum is recovered.
I de fleste tilfælde udvindes molybdænet i en kemisk 5 form, der kræver yderligere, komplicerede procestrin til omdannelse til de forskellige forbindelser, der anvendes i praksis.In most cases, the molybdenum is recovered in a chemical form that requires additional, complicated process steps to convert to the various compounds used in practice.
I britisk patentskrift nr. 743 367 omtales et eksempel på en sådan yderligere oparbejdning, nemlig konverte-10 ring af vandige natrium-, kalium- eller ammoniummolyb- datopløsninger til en koncentreret molybdænsyrehydrosol indeholdende 40 - 300 g molybdænoxid pr. liter, som gennemføres ved, at den vandige, fortrinsvis svagt ammonia-kalske, molybdatopløsning sendes gennem en syrevasket 15 kationbytter.British Patent Specification No. 743,367 discloses an example of such further work-up, namely the conversion of aqueous sodium, potassium or ammonium molybdate solutions to a concentrated molybdic acid hydrosol containing 40-300 g of molybdenum oxide per liter. per liter, which is carried out by passing the aqueous, preferably weakly ammonia-calcium molybdate solution, through an acid washed 15 cation exchanger.
Den til grund for opfindelsen liggende opgave går ud på at tilvejebringe en fremgangsmåde af den indledningsvis angivne art, som kan gennemføres på enkel og økonomisk måde, og som giver praktisk taget kvantitativt 20 udbytte.The object of the invention is to provide a method of the kind described in the introduction which can be carried out in a simple and economical manner and which gives practically quantitative yield.
Opfindelsen angår specielt genvinding af molybdæn i form af en vandig opløsning af ren molybdænsyre fra brugte katalysatorer anvendt ved oxidation af methanol til formaldehyd, som væsentligt består af molybdæn-25 og jernoxider.The invention relates in particular to the recovery of molybdenum in the form of an aqueous solution of pure molybdenum acid from spent catalysts used in the oxidation of methanol to formaldehyde, which consists essentially of molybdenum and iron oxides.
Herudover tilsigter opfindelsen at tilvejebringe en genvinding af molybdæn i form af en vandig opløsning af ren molybdænsyre fra brugte hydrogeneringskatalysatorer, der er understøttet eller ikke understøttet og 30 indeholder molybdænoxid sammen med et eller flere yder ligere metaloxider, specielt cobalt- og/eller nikkeloxid .In addition, the invention aims to provide a recovery of molybdenum in the form of an aqueous solution of pure molybdenum acid from spent hydrogenation catalysts supported or unsupported and containing molybdenum oxide together with one or more additional metal oxides, especially cobalt and / or nickel oxide.
44
DK 155020 BDK 155020 B
Denne opgave løses ifølge opfindelsen ved en fremgangsmåde af den indledningsvis angivne art, som er ejendommelig ved, at der fremstilles en vandig natrium-molybdatopløsning indeholdende fra 2 til 20 vægt-% Mo 5 med en pH-værdi på fra 9,5 til 13, som i det andet trin konverteres direkte til en ren vandig molybdænsyre-opløsning ved perkolering gennem en stærk kationbytter-harpiks på hydrogenform med en hastighed på fra 0,5 til 3 rumfang pr. rumfang harpiks og pr. time ved en 10 temperatur på fra 10 til 80 °C.This object is solved according to the invention by a process of the kind described in the beginning, characterized in that an aqueous sodium molybdate solution containing from 2 to 20% by weight Mo 5 having a pH of from 9.5 to 13 is prepared, which in the second step is converted directly to a pure aqueous molybdic acid solution by percolation through a strong cation exchange resin in hydrogen form at a rate of from 0.5 to 3 volumes per volume of resin and per. hour at a temperature of from 10 to 80 ° C.
I modsætning til den kendte teknik genvindes molybdæn med særdeles højt udbytte og på særdeles enkel måde, idet andet trin gennemføres i én arbejdsgang.Contrary to the prior art, molybdenum with very high yield and in very simple manner is recovered, the second step being carried out in one operation.
Den således fremstillede molybdænsyre kan herefter omdan-15 nes til ønskede salte ved behandling med passende baser.The molybdenum acid thus produced can then be converted to desired salts by treatment with appropriate bases.
Før gennemføringen af fremgangsmåden ifølge opfindelsen formales katalysatorerne fortrinsvis til et pulver med en finhed .af størrelsesordenen 300 ^um.Prior to carrying out the process of the invention, the catalysts are preferably ground to a powder of a magnitude of the order of 300 µm.
Sommetider har en varmebehandling af disse pulvere vist 20 sig fordelagtig og en opvarmning, når det f. eks. drejer sig om katalysatorer, der er anbragt på aluminiumoxid, ved 900 - 1000 °C i et tidsrum på en til flere timer, bevirker, at aluminiumoxidet ikke angribes eller i det væsentlige ikke angribes af alkalimetalhydroxidet.Sometimes a heat treatment of these powders has proved advantageous and a heating, for example, in the case of catalysts mounted on alumina at 900-1000 ° C for a period of one to several hours, causes the alumina is not attacked or substantially attacked by the alkali metal hydroxide.
25 Den brugte, formalede og eventuelt varmebehandlede kata lysator behandles med en vandig opløsning af et alkali-metalhydroxid. Fortrinsvis anvendes der til dette formål vandig natriumhydroxid i en koncentration på fra 2 til 15 vægt-?i. Behandlingen udføres ved stuetemperatur (20 -30 25 °C), sædvanligvis uden ydre tilførsel af varme.The spent, ground and optionally heat treated catalyst is treated with an aqueous solution of an alkali metal hydroxide. Preferably, for this purpose, aqueous sodium hydroxide is used at a concentration of from 2 to 15% by weight. The treatment is carried out at room temperature (20-30 ° C), usually without external heat supply.
55
DK 155020 BDK 155020 B
Det er imidlertid muligt at arbejde ved højere temperaturer end stuetemperatur, f. eks. ved indtil 70 °C.However, it is possible to operate at higher temperatures than room temperature, for example at up to 70 ° C.
Når der arbejdes under disse betingelser og et tidsrum på 1 - 4 timer solubiliseres molybdænet i form af alkali-5 metalmolybdat, medens de andre metaller som f. eks.When operating under these conditions and for a period of 1-4 hours, the molybdenum in the form of alkali metal molybdate is solubilized, while the other metals such as e.g.
jern, cobalt og nikkel udfælder i form af hydroxider.iron, cobalt and nickel precipitate in the form of hydroxides.
Opløsningen, der bliver tilbage efter filtreringen, samt eventuelt vaskevand bringes derpå i kontakt med en stærk kationbytterharpiks i syreformen, også kaldet 10 hydrogenformen.The solution remaining after the filtration, as well as any wash water, is then brought into contact with a strong cation exchange resin in the acid form, also called the hydrogen form.
Velegnede stærke kationbytterharpikser er de, der bærer sulfon- eller methylensulfongrupper. Blandt de sidstnævnte er den vigtigste ionbytterharpiks fremstillet ved sulfonering af polystyren tværbundet med divinyl-15 benzen.Suitable strong cation exchange resins are those carrying sulfone or methylene sulfone groups. Among the latter, the most important ion exchange resin is made by sulfonating polystyrene crosslinked with divinylbenzene.
Ionbytterharpikser, der er velegnede til anvendelse ved fremgangsmåden ifølge opfindelsen, har sædvanligvis en ombytningskapacitet på fra 1 til 3 udtrykt i ækvivalenter pr. liter harpiks. Eksempler på velegnede 20 kommercielt tilgængelige harpikser er "DU0LITE" C 264 og "DU0LITE" C 265 (fra the Chemical Process Company), "AMBERLITE" IR 124 (fra Rohm & Haas Company) og lignende.Ion exchange resins suitable for use in the process of the invention usually have an exchange capacity of from 1 to 3 expressed in equivalents per minute. liter of resin. Examples of suitable 20 commercially available resins are "DUOLITE" C 264 and "DUOLITE" C 265 (from the Chemical Process Company), "AMBERLITE" IR 124 (from Rohm & Haas Company) and the like.
Ifølge en foretrukken udførelsesform for opfindelsen arrangeres harpiksen i form af et fast leje og efter 25 eventuel konditionering og behandling for at omdanne lejet til syreformen, perkoleres den vandige opløsning af natriummolybdat gennem lejet. Normalt udføres behandlingen ved stuetemperatur (20 - 25 °C), selv om det er muligt at anvende et bredere temperaturområde som 30 f. eks. fra 10 til 80 °C.According to a preferred embodiment of the invention, the resin is arranged in the form of a fixed bed and after any conditioning and treatment to convert the bed to the acid form, the aqueous solution of sodium molybdate is percolated through the bed. Usually, the treatment is carried out at room temperature (20 - 25 ° C), although it is possible to use a wider temperature range such as 30, for example, from 10 to 80 ° C.
Når der arbejdes under disse betingelser, opnås der 6When working under these conditions, 6 are obtained
DK 155020 BDK 155020 B
en vandig opløsning af molybdænsyre, der kan anvendes som den er eller efter omdannelse til det ønskede salt ved behandling med en passende base. Efter vask med vand og behandling med en syre (svovlsyre, saltsyre 5 eller lignende syrer) for at overføre den til syreformen, kan harpiksen atter anvendes til en ny behandling.an aqueous solution of molybdenum acid which can be used as is or after conversion to the desired salt by treatment with a suitable base. After washing with water and treating it with an acid (sulfuric acid, hydrochloric acid or similar acids) to transfer it to the acid form, the resin can be used again for a new treatment.
Således muliggør fremgangsmåden ifølge opfindelsen fremstillingen af molybdæn i form af molybdænsyre på en bekvem og økonomisk måde.Thus, the process of the invention enables the preparation of molybdenum in the form of molybdenum acid in a convenient and economical manner.
10 Fremgangsmåden ifølge opfindelsen omfatter en simpel perkolering af en vandig opløsning af et alkalimetal- * salt af molybdænsyre (sædvanligvis natriummolybdat) gennem en stærk ionbytterharpiks i hydrogenformen, Ved hjælp af denne perkolering fås der stærkt sure opløsnin-15 ger, der er svagt blå (molybdænblåt), der kan nå særde les høje koncentrationer (i størrelsesordenen 80 g/liter udtrykt som metallisk molybdæn). Disse opløsninger, der har en meget lav pH-værdi (af størrelsesordenen 1,5), er særdeles stabile gennem længere tid og kan 20 anvendes til fremstilling af alle mulige molybdater.The process of the invention comprises a simple percolation of an aqueous solution of an alkali metal salt of molybdenic acid (usually sodium molybdate) through a strong ion exchange resin in the hydrogen form. By this percolation strongly acidic solutions which are slightly blue ( molybdenum blue), which can reach very high concentrations (in the order of 80 g / liter expressed as metallic molybdenum). These solutions, which have a very low pH (of the order of 1.5), are extremely stable over a long period of time and can be used to prepare all kinds of molybdenum.
Det skal bemærkes, at opløsningerne, afhængigt af pH-vær-dien, der kan indstilles ved tilsætning af base, kan indeholde forskellige molybdænpolysyrer.It should be noted that, depending on the pH value which can be adjusted by the addition of base, the solutions may contain different molybdenum polyacids.
Molybdænindholdet i de ved fremgangsmåden ifølge opfin-25 delsen opnåede opløsninger bestemmes ved titrering med opløsninger, der har et kendt indhold af natriumhydroxid.The molybdenum content of the solutions obtained by the process of the invention is determined by titration with solutions having a known sodium hydroxide content.
Ved at anvende et pH-meter til titreringen, er det muligt at bestemme neutraliseringspunktet for syrens to hydrogenatomer .By using a pH meter for the titration, it is possible to determine the neutralization point of the two hydrogen atoms of the acid.
30 I det følgende belyses opfindelsen nærmere ved en række eksempler.In the following, the invention is further illustrated by a number of examples.
77
DK 155020 BDK 155020 B
I eksemplerne anvendes der en stærk kationbytterharpiks, der kommercielt kendes under navnet "DUOLITE" C 264(fra the Chemical Process Company), og som har følgende egenskaber: Matrixen består af makroporøst polystyren tvær-5 bundet med divinylbenzen, der bærer sulfongrupper -SO^H, størrelsen af harpiksgranulerne er omkring 0,3-1,2 mm og ombytningskapaciteten er ca. 2,5 ækvivalenter pr. liter.In the examples, a strong cation exchange resin, known commercially under the name "DUOLITE" C 264 (from the Chemical Process Company), is used and has the following properties: The matrix consists of macroporous polystyrene cross-linked with divinylbenzene carrying sulfone groups -SO H, the size of the resin granules is about 0.3-1.2 mm and the exchange capacity is approx. 2.5 equivalents per liter.
Inden anvendelsen konditioneres harpiksen og omdannes 10 til hydrogenformen ved hjælp af følgende metode: 1) Konditionering i afioniseret vand i 10-15 timer og efterfølgende vask, stadig med afioniseret vand, af det fremstillede harpiksleje; 2) behandling med en stærk syre (f.eks. HC1, h^SO^, 15 HNO^) i vandig opløsning med en syrekoncentration i området 2-40 vægt-% med en hastighed på 2-8 rumfang syreopløsning pr. rumfang harpiks og pr. time; 3) vask med afioniseret vand indtil pH-værdien er neutral med en hastighed på 10-20 rumfang vand pr. rumfang 20 harpiks og pr. time.Prior to use, the resin is conditioned and converted to the hydrogen form by the following method: 1) Conditioning in deionized water for 10-15 hours and subsequent washing, still with deionized water, of the prepared resin bed; 2) treatment with a strong acid (eg HCl, h 2 SO volume of resin and per. hour; 3) washing with deionized water until the pH is neutral at a rate of 10-20 volumes of water per day. volume of 20 resin and per. hour.
Efter anvendelsen udføres regenereringen af harpiksen til hydrogenformen ved at gentage behandlingerne 2 og 3 som angivet ovenfor.After use, the regeneration of the resin to the hydrogen form is performed by repeating treatments 2 and 3 as indicated above.
EKSEMPEL 1 25 Molybdæn genudvindes fra en anvendt katalysator, der er blevet brugt til oxidering af methanol til formaldehyd, og som består af molybdæn-, jern- og cobaltoxider med 81,5 vægt-?o molybdænoxid.EXAMPLE 1 Molybdenum is recovered from a used catalyst which has been used to oxidize methanol to formaldehyde and consists of molybdenum, iron and cobalt oxides with 81.5% by weight molybdenum oxide.
DK 155020 BDK 155020 B
88
Den ovenfor omtalte katalysator formales for at reducere den til pulver af størrelsesordenen 300 ^um, og pulveret tørres ved opvarmning ved 200 °C i 2 timer.The catalyst mentioned above is ground to reduce it to powder of the order of 300 µm and the powder is dried by heating at 200 ° C for 2 hours.
300,2 g af det tørrede pulver behandles med 1132 g af 3 en vandig opløsning indeholdende 12 vægt-% natriumhy droxid. Hele massen holdes i kontakt under omrøring i 2 timer ved stuetemperatur (20-25 °C). Den faste rest filtreres fra og vaskes. Herved fås 1400 ml vandig opløsning med en pH-værdi på ca. 10,5, der indeholder 163 10 g molybdæn udtrykt som metal, svarende til en Mo-koncen- tration på ca. 10 vægt-%. Den faste rest, der vejer 55,5 g, består i det væsentlige af jern- og cobalt-hydroxider. Den fremstillede opløsning perkoleres gennem 4 liter ionbytterharpiks i syreformen som omtalt ovenfor 15 med en hastighed på 1 rumfang opløsning pr. rumfang harpiks og pr. time. Efter perkoleringen er gennemført, vaskes søjlen med afioniseret vand, og den perkolerede opløsning og vaskevandet slås sammen. Herved fås 4 liter vandig opløsning bestående af molybdænsyre indeholdende 20 ca. 41 g/liter molybdæn. Totalgenudvindelsesudbyttet af molybdæn er således lig med 100%.300.2 g of the dried powder is treated with 1132 g of 3 an aqueous solution containing 12 wt% sodium hy droxide. The whole mass is kept in contact with stirring for 2 hours at room temperature (20-25 ° C). The solid residue is filtered off and washed. This gives 1400 ml of aqueous solution with a pH of approx. 10.5 containing 163 10 g of molybdenum expressed as metal, corresponding to a Mo concentration of approx. 10% by weight. The solid residue weighing 55.5 g consists essentially of iron and cobalt hydroxides. The solution prepared is percolated through 4 liters of ion exchange resin in the acid form as discussed above at a rate of 1 volume of solution per ml. volume of resin and per. hour. After the percolation is complete, the column is washed with deionized water and the percolated solution and the wash water are combined. Thereby, 4 liters of aqueous solution consisting of molybdic acid containing 20 ca. 41 g / liter molybdenum. Thus, the total recovery yield of molybdenum is equal to 100%.
Den fremstillede molybdænsyre omdannes til ammonium-paramolybdat, der anvendes som udgangsmateriale til fremstilling af katalysatorer til oxidering af methanol 25 til formaldehyd.The molybdenumic acid produced is converted to ammonium paramolybdate used as a starting material for the preparation of catalysts for the oxidation of methanol 25 to formaldehyde.
EKSEMPEL 2EXAMPLE 2
Man går frem som i eksempel 1, men anvender 328 g katalysator, der er formalet og tørret. Behandlingen af pulveret udføres med 1237,6 g vandig natriumhydroxid 30 med en koncentration på 12 vægt-%. Efter fraskillelse og vask af den faste rest, fås der 1500 ml natriummolyb-datopløsning med en pH-værdi på ca. 10,5, der indehol- 9Proceed as in Example 1, but use 328 g of catalyst which is ground and dried. The treatment of the powder is carried out with 1237.6 g aqueous sodium hydroxide 30 at a concentration of 12% by weight. After separation and washing of the solid residue, 1500 ml of sodium molybdate solution with a pH of approx. 10.5 containing 9
DK 155020 BDK 155020 B
der 178,1 g molybdæn, svarende til en Mo-koncentration på ca. 10 vægt-%.there are 178.1 g of molybdenum, corresponding to an Mo concentration of approx. 10% by weight.
Opløsningen perkoleres gennem 4 liter harpiks, der er regenereret efter anvendelsen i eksempel 1, med en has-5 tighed på 1 rumfang opløsning pr. rumfang harpiks og pr. time. Efter at perkoleringen er gennemført, vaskes søjlen med afioniseret vand, og der fås ialt 5 liter vandig opløsning af molybdænsyre indeholdende 35,6 g/liter molybdæn udtrykt som metal. Perkoleringen og vasken 10 udføres ved stuetemperatur (20-25 °C). Totaludbyttet for genudvindelse af molybdæn er lig med 100%.The solution is percolated through 4 liters of resin regenerated after use in Example 1 at a rate of 1 volume of solution per liter. volume of resin and per. hour. After the percolation is completed, the column is washed with deionized water and a total of 5 liters of aqueous solution of molybdenum acid containing 35.6 g / liter molybdenum expressed as metal is obtained. The percolation and wash 10 are carried out at room temperature (20-25 ° C). The total yield for the recovery of molybdenum is 100%.
Den fremstillede molybdænsyreopløsning lagredes i en kold beholder fremstillet af gennemskinneligt glas og udsattes for lys. Efter 3 måneders lagring viste opløs-15 ningen ikke nogen forandring.The prepared molybdenumic acid solution was stored in a cold container made of translucent glass and exposed to light. After 3 months of storage, the solution showed no change.
EKSEMPEL 3EXAMPLE 3
Man går frem som i eksempel 1 og anvender 304,1 g katalysator, der er tørret og formalet. Pulveret behandles med 1147,5 g vandig natriumhydroxid i en koncentration 20 på 12 vægt-%. Efter fraskillelse og vask af den faste rest, fås der 1400 ml natriummolybdatopløsning med en pH-værdi på ca. 10,5, der indeholder 165,15 g molybdæn, svarende til en Mo-koncentration på ca. 10 vægt-%.Proceed as in Example 1 and use 304.1 g of dried and ground catalyst. The powder is treated with 1147.5 g aqueous sodium hydroxide at a concentration of 20% by weight. After separation and washing of the solid residue, 1400 ml of sodium molybdate solution with a pH of approx. 10.5 containing 165.15 g molybdenum, corresponding to a Mo concentration of approx. 10% by weight.
Opløsningen perkoleres gennem 4 liter harpiks, der er 25 regenereret efter anvendelsen i eksempel 2, med en has tighed på 1 rumfang opløsning pr. rumfang harpiks og pr. time. Efter at perkoleringen er afsluttet, vaskes søjlen med afioniseret vand, og der fås ialt 4,5 liter vandig opløsning af molybdænsyre, der indeholder 36,7 30 g/liter molybdæn udtrykt som metal. Perkoleringen ogThe solution is percolated through 4 liters of resin which has been regenerated after use in Example 2, at a rate of 1 volume solution. volume of resin and per. hour. After the percolation is complete, the column is washed with deionized water and a total of 4.5 liters of aqueous solution of molybdenum acid containing 36.7 30 g / liter molybdenum expressed as metal is obtained. The percolation and
DK 155020 BDK 155020 B
10 vasken udføres ved stuetemperatur (20-25 °C).The wash is performed at room temperature (20-25 ° C).
Totaludbyttet for genudvindelsen af molybdæn er lig med 100¾. Molybdænsyreopløsningen behandles med vandig ammoniak, og det fremstillede ammoniummolybdat anvendes 5 til fremstilling af en hydrogeneringskatalysator, der er baseret på molybdæn- og cobaltoxider understøttet af aluminiumoxid.The total yield for the recovery of molybdenum is equal to 100¾. The molybdic acid solution is treated with aqueous ammonia and the ammonium molybdate produced is used to prepare a hydrogenation catalyst based on alumina supported by alumina.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2822379A IT1127300B (en) | 1979-12-19 | 1979-12-19 | PROCEDURE FOR THE RECOVERY OF MOLYBDENUM COMPOUNDS |
| IT2822379 | 1979-12-19 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK539380A DK539380A (en) | 1981-06-20 |
| DK155020B true DK155020B (en) | 1989-01-23 |
| DK155020C DK155020C (en) | 1989-06-05 |
Family
ID=11223176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK539380A DK155020C (en) | 1979-12-19 | 1980-12-18 | PROCEDURE FOR RECOVERING MOLYBDA IN THE FORM OF Aqueous SOLUTION OF PURE MOLYBDAIC ACID FROM MOLYBDA-CONTAINING CATALYSTS |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4401631A (en) |
| AT (1) | AT376637B (en) |
| BR (1) | BR8008243A (en) |
| DE (1) | DE3047592A1 (en) |
| DK (1) | DK155020C (en) |
| ES (1) | ES497646A0 (en) |
| FR (1) | FR2472030B1 (en) |
| GB (1) | GB2065628B (en) |
| IN (1) | IN153915B (en) |
| IT (1) | IT1127300B (en) |
| NL (1) | NL8006780A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666685A (en) * | 1986-05-09 | 1987-05-19 | Amax Inc. | Selective extraction of molybdenum and vanadium from spent catalysts by oxidative leaching with sodium aluminate and caustic |
| FR2687170B1 (en) * | 1992-02-07 | 1994-09-30 | Eurecat Europ Retrait Catalys | RECOVERY OF MOLYBDENE AND VANADIUM FROM USED CATALYSTS. |
| US5736112A (en) * | 1995-05-08 | 1998-04-07 | Huntsman Specialty Chemicals Corporation | Aqueous oxidation of organic molybdenum compounds |
| TW576825B (en) * | 2000-08-10 | 2004-02-21 | Iner Ae | Method for liquid chromate ion and oxy-metal ions removal and stabilization |
| DK2064358T3 (en) * | 2006-09-14 | 2012-11-26 | Albemarle Netherlands Bv | Process for recovery of group vi-b metals from spent catalysts |
| CL2009000939A1 (en) * | 2008-04-30 | 2010-10-01 | Evonik Degussa Gmbh | Process to recover molybdate or tungstate from an aqueous solution that comprises a) contacting the solution with a cationized and water-insoluble inorganic carrier material, b) separating the carrier material from molybdate or tungstate, c) contacting it with an aqueous solution with a pH between 6 to 14 and d) separate the saturated material. |
| EP2113575A1 (en) * | 2008-04-30 | 2009-11-04 | Evonik Degussa GmbH | Method of recovering molybdat and wolframat from aqueous solutions |
| DE102010001001A1 (en) | 2010-01-19 | 2011-07-21 | Evonik Degussa GmbH, 45128 | Process for delignification and bleaching of pulp |
| CN105723028A (en) | 2013-11-06 | 2016-06-29 | 赢创德固赛有限公司 | Method for delignifying and bleaching pulp |
| CN116022848A (en) * | 2022-12-06 | 2023-04-28 | 西安诺博尔稀贵金属材料股份有限公司 | By using molybdenum copper alloy scrap production of molybdic acid method for preparing sodium compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB743367A (en) * | 1953-08-14 | 1956-01-11 | Exxon Research Engineering Co | Improvements in or relating to molybdena hydrosols |
| DE2631089A1 (en) * | 1976-07-10 | 1978-01-12 | Degussa | Molybdenum recovery from spent catalyst - by impregnating with caustic soda, calcining the impregnated catalyst and transferring to water to form molybdate |
| US4145397A (en) * | 1976-08-06 | 1979-03-20 | Marubeni Corporation | Process for recovering molybdenum, vanadium, cobalt and nickel from roasted products of used catalysts from hydrotreatment desulfurization of petroleum |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957946A (en) * | 1974-12-23 | 1976-05-18 | Amax Inc. | Molybdenum oxide purification process |
| NL7504500A (en) * | 1975-04-16 | 1976-10-19 | Akzo Nv | PROCEDURE FOR THE SEPARATE WINNING OF VANADIUM AND MOLYBDEEN. |
| JPS5252895A (en) * | 1975-10-28 | 1977-04-28 | Mitsui Mining & Smelting Co Ltd | Process for recovering molybdenum from waste catalyst of desulfurnizat ion |
| US4046852A (en) * | 1976-05-19 | 1977-09-06 | Amax Inc. | Purification process for technical grade molybdenum oxide |
| US4079116A (en) * | 1976-12-27 | 1978-03-14 | Amax Inc. | Process for producing ammonium heptamolybdate and/or ammonium dimolybdate |
| US4199551A (en) * | 1978-01-13 | 1980-04-22 | Amax Inc. | Recovery of molybdenum and uranium from activated charcoal containing molybdenum and residual uranium |
-
1979
- 1979-12-19 IT IT2822379A patent/IT1127300B/en active
-
1980
- 1980-12-11 GB GB8039673A patent/GB2065628B/en not_active Expired
- 1980-12-12 ES ES497646A patent/ES497646A0/en active Granted
- 1980-12-15 NL NL8006780A patent/NL8006780A/en active Search and Examination
- 1980-12-16 BR BR8008243A patent/BR8008243A/en unknown
- 1980-12-17 DE DE19803047592 patent/DE3047592A1/en active Granted
- 1980-12-18 DK DK539380A patent/DK155020C/en not_active IP Right Cessation
- 1980-12-18 FR FR8026957A patent/FR2472030B1/fr not_active Expired
- 1980-12-18 AT AT619080A patent/AT376637B/en not_active IP Right Cessation
- 1980-12-19 IN IN1408/CAL/80A patent/IN153915B/en unknown
- 1980-12-19 US US06/218,225 patent/US4401631A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB743367A (en) * | 1953-08-14 | 1956-01-11 | Exxon Research Engineering Co | Improvements in or relating to molybdena hydrosols |
| DE2631089A1 (en) * | 1976-07-10 | 1978-01-12 | Degussa | Molybdenum recovery from spent catalyst - by impregnating with caustic soda, calcining the impregnated catalyst and transferring to water to form molybdate |
| US4145397A (en) * | 1976-08-06 | 1979-03-20 | Marubeni Corporation | Process for recovering molybdenum, vanadium, cobalt and nickel from roasted products of used catalysts from hydrotreatment desulfurization of petroleum |
Also Published As
| Publication number | Publication date |
|---|---|
| IT7928223A0 (en) | 1979-12-19 |
| AT376637B (en) | 1984-12-10 |
| IN153915B (en) | 1984-08-25 |
| DE3047592A1 (en) | 1981-09-17 |
| ES8200726A1 (en) | 1981-11-16 |
| ATA619080A (en) | 1984-05-15 |
| DE3047592C2 (en) | 1988-08-25 |
| ES497646A0 (en) | 1981-11-16 |
| FR2472030B1 (en) | 1983-06-17 |
| GB2065628B (en) | 1984-05-16 |
| IT1127300B (en) | 1986-05-21 |
| DK539380A (en) | 1981-06-20 |
| BR8008243A (en) | 1981-07-07 |
| GB2065628A (en) | 1981-07-01 |
| DK155020C (en) | 1989-06-05 |
| FR2472030A1 (en) | 1981-06-26 |
| US4401631A (en) | 1983-08-30 |
| NL8006780A (en) | 1981-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7061816B2 (en) | Clean molybdenum metallurgy method | |
| CA2783646C (en) | Process for recovery of precious metals | |
| DK155020B (en) | PROCEDURE FOR RECOVERING MOLYBDA IN THE FORM OF Aqueous SOLUTION OF PURE MOLYBDAIC ACID FROM MOLYBDA-CONTAINING CATALYSTS | |
| CN101376923B (en) | Method for recycling noble metal from spent catalyst | |
| NO884023L (en) | PROCEDURE FOR SCANDIUM EXPLORATION. | |
| KR20070015388A (en) | Method for recovering molybdenum and method for preparing catalyst | |
| NL2005158C2 (en) | Process for isolating vanadium from a solid composition. | |
| WO2000071248A1 (en) | Process for producing catalyst | |
| EP1728764A1 (en) | Process for the production of lead hydrate or monoxide of high purity from materials and/or residues containing lead in the form of sulphates, monoxides and/or other compounds | |
| JPS5850775B2 (en) | Production method of copper-iron-aluminum catalyst | |
| JPS6219494B2 (en) | ||
| US4075277A (en) | Process for recovering molybdenum values from spent catalysts | |
| WO2020138137A1 (en) | Method for purifying vanadium oxide | |
| JPS59102821A (en) | Manufacture of chromium (iii) compound | |
| CN105688877B (en) | Iron-based catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| US8318005B2 (en) | Tetra-sulfo iron-phthalocyanine and related methods | |
| JPS6034927A (en) | Purification of cyclohexanone containing organic acid as by-product | |
| US4331567A (en) | Process for preparing catalysts based on molybdenum and iron oxides | |
| CN113215419A (en) | Method for extracting valuable elements from waste SCR denitration catalyst | |
| KR20000001579A (en) | Separation and recovery of nickel, vanadium, and molybdenum from waste catalyst of vacuum residue desulfurization | |
| KR920010086B1 (en) | Method of producing crystalline ammonium metatungstate | |
| CN111298846A (en) | Method for recovering waste iron-molybdenum catalyst for preparing formaldehyde by oxidizing methanol | |
| GB1585842A (en) | Process for recovering molybdenum vanadium cobalt and nickel from roasted products of used catalysts from hydrotreatment desulphurization of petroleum | |
| US11623870B2 (en) | Methods that purify uranium | |
| JPH10130181A (en) | Production of ethylene oxide adduct |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |